Diallyl ether dichlorohydrins



i atented Mar. 6,

UNITED" STATES PATENT OF ,DIALLYL ii'rrmifl i r zijnoitommtmg Owen Clement Wentworth Allenby, McMasterville, Quebec; Qanada, assignor to Canadian Industries Limited, Montre'al; Quebec; Canada; a. corporation of. Quebec;Canada; I

No Drawing. Application March 1948, Serial No 13334; InJCanada'Aiigus't 8,1947

. 1 -'Ihis invention relatesto new compositions of matter, and, more particularly, diallyl ether dichlorohydrins, and to a method for their preparation;

In United States Patent No. 2,314,039, there is disclosed dial-lyl ether monochloroh-ydrin together withv a method; for its preparation which com prises reacting epichlorohydrinwith allyl alcohol in the presence of boron trifluoride as a cat'alyst. The monochlorhydrin thus obtained has the following formula:

CHzi-GHw-G 0- UH=C Hi 1 on Diallyl ether can also be reacted with hyiio 'm rous acid to prepare the same compound, which case two i's'oiiijrs may be obtaihed havifi the formula:

om( ri-om o -ori -on=om X Y v wherein X and? may" be chlorine and h drexyi, X being chlorine when Y is hydroxyl and Y being chlorine when X is hydroxyl It is angob'ject' of this invention to provide new addition products of diallyl ether; monochloi'oe 'hyd'rihs. Another object isth provision-of dia yl ether dichlorohydrlns, said dichlorohydrinsfbeifig" new and userui compounds; A further object is the preparation of diallyl ether-dichlorohyd'rihs. Other objects will-appear hereinafter.

These objects are accomplished byreacting" comprises reacting a dispersion of diall-yl ether 1 "cats; (01. zoo-e15.)

monochlorohydri ns" in dilute mineral. acid, siich as Sulphuric acid, With'an aqueous sblll-tlbfidf a; hypochlo'rite, said hypochl'orite solution being added slowly to the diallyl ether monochloro hydrins acid dispersion. The hypochl'orous-acid liberated by the interaction or the mineral acid and thehypo'chlorite reacts with the dialiyi ether monoch lorohydrins to" form the' dichlorohydrin's" An alternative procedure is to reacta dispersionof diallyl ether monochlorohydri ns ai'hypochlorite with astrong mineral acid. Thediallyl V v 2; V chlorine when Y an Y are hydroxyl and Y and Y being chlorine when X and-X are hy'drox'yl.

The following examples are illustrative of the more detailed practice of this invention:

Example 1 48- grams of diallyl ether monochlorohydrin, prepared by reacting epichlorohydrin; with allyl alcohol, was placed in'a 5-liter flask containing 1900 milliliters of a sodium hypochlorite solution. The latter was prepared by adding 27.5; grams of chlorine slowly at 2 Cato I060 milliliters of. water containing 31 grams of sodium hydroxide; To the stirred mixture of sodium hypochlorite and diallyl ether monochlorohydrin, 200 milliliters of Water containing 11' grams: of 95.5% sulphuric acid was added at 10 C. over a period of 20 minutes; The excess hypochlorite was destroyed with sodium sulphite. A total of 16.8 grams of hypochlorous acid-wasshown to have been taken up. by addition to the double bond in the diallyl ether monochloroh y drins, 17.5 grams being; the theoretical required. The dichlorohydrins so produced were extracted five times with a. total or 5 liters of ethylene dichloride. The solvent wasthenevaporated. off and the dichlorohydrins residue weighed42 grams; representing a yield of .1 r

The alcove diallyl ether dichlorohydrins were dehydrochlorinated to the dioxide by stirring for "15 minutes at 20? G. with 200 milliliters qt 9, 10% aqueous solution of sodium hydroxides The dioxide was removed loy extractin v three times with a total of 3v liters of carbon tetrachloride. The solvent-was evaporated and the residue distilled. A 63% yield (17 grams) of diallylether dioxide was obtained; This compound had a density of 1 .1229- and a refractive index of 1.4452 at 23 Cr Its molectrlarrefractivity was calculated 30.89 and found- 30.84; and the analyses: carbon. calculated 55.4%, found 5455% hydrogen calculated. 751% found 7.63%; The boiling point oi the purified material: was found to be 86-87.5 C. at 5' mm. pressure.-.

Example 2 To 50 grams of diallyl. ether monochlorohydrin, prepared by the interaction of epichlororavens and allyl alcohol and dispersedin milliliters oi a 25% adueoussoliit'ion of sulphuric acid, there was'added 670. milliliters of a sodium hypochlorite solution titrating 2.7% as hypochlorous acid; at 1050i over a 20 minute period and with good; stirring. I H

100' milliliters of a; 35% aqueous solution of A dispersion of 50 grams of diallyl ether monochlorohydrin, prepared from epichlorohydrin and allyl alcohol, in 200 milliliters of a 10% aqueous solution of sulphuric acid was placed in a 2-liter flask, and 570 milliliters of a sodium hypochlorite solution, titrating 3.2% as hypochlorous acid, was added thereto at 10 C. over a 20 minute period with good stirring.

The above mixture was afterwards shaken for v minutes at 10 C. with 1'00 milliters of a 35% aqueous solution of sodium hydroxide. The mixture was then placed in a continuous extractor for 2 hours with carbon tetrachloride, after which time the solvent was evaporated from the extract and the residue of said extract distilled at 70-90 C. under a 1.0-1.5 mm. pressure. 17.4 grams of .diallyl ether dioxide was thus isolated, i e., a 40% yield based on the weight of monochlorohydrin present in the reaction mixture.

Example 4 50 grams of diallyl ether monochlorohydrin, prepared by reacting .epichlorohydrin with allyl alcohol, was dispersed in 200 milliliters of a 10% aqueous solution of sulphuric acid, and 365 milliliters of a sodium hypochlorite solution, titrating 4.0% as hypochlorous acid, was added thereto at 10 C. over a minute period with continuous stirring.

100 milliliters of a 35% aqueous solution of sodium hydroxide was added to the above mixture and the stirring was continued at 15 C. for 20 minutes. The mixture'was-then transferred to. a continuous extractor and therein treated with carbon tetrachloride for 4 hours. After evaporation of the carbon tetrachloride from the extract, the residue was distilled at 80-90 C. under a 1 mm. pressure thus liberating 25.2 grams of diallyl ether dioxide, i. e., a 58% yield based on the amount of diallyl ether monochlorohydrin used.

Example 5 To a dispersion of grams of diallyl ether monochlorohydrin, obtained from epi-chlorohydrin and allyl alcohol, in 100 milliliters of a 20% aqueous solution of sulphuric acid, there was added 370 milliliters of a sodium hypochlorite solution, titrating 4.0% as hypochlorous acid, said addition being made at 10 C. over a 20 minute period and with continuous stirring of the dispersion.

The above mixture was then treated at 10 C. for 10 minutes with 200 milliliters of carbon tetrachloride and 100 milliliters of a 35% aqueous solution of sodium hydroxide. There was a formation of two layers at this stage. The nonaqueous layer was submitted to evaporation to remove carbon tetrachloride and the residue was to yield 6.1 grams of diallyl ether dioxide. The

aqueous layer was re-extracted for 4 hours with carbon tetrachloride, and, after removal of carbon tetrachloride and distillation of the residue at 70-90 C. under a 1.0-1.5 mm. pressure, 14.2 grams of diallyl ether dioxide was isolated. There was thus obtained a total of 20.3 grams of diallyl ether dioxide, i. e., a 47% yield based on the weight of monochlorohydrin present in the reaction mixture.

Example 6 grams of chlorine was passed into 1 liter of a 9.5% aqueous solution of sodium hydroxide at 1 C., and the sodium hypochlorite solution thus obtained, titrating 56% as hypochlorous acid, was added at 15 C. over a 20 minute period to a dispersion of grams of diallyl ether vmonochlorohydrin (obtained from epichlorohydrin and allyl alcohol) in 200 milliliters of a 16% aqueous solution of sulphuric acid. 920 milliliters of the hypochlorite solution was required before a positive test for hypochlorous acid was obtained in the reaction vessel.

200 milliliters of a 47% aqueous solution of sodium hydroxide was then added to the above mixture, which was stirred at 15 C. for 15 minutes. The mixture was afterwards extracted five times with a total of 5 liters of carbon tetrachloride, and, after removal of the solvent, the residue was distilled at 80-90 C. under a 1 mm. pressure. 72 grams of diallyl ether dioxide was thus obtained, 1. e., a 55% yield based on the diallyl ether monochlorohydrin used. f

Although other ratios may be used, it is preferred to use equimolar proportions of diallyl ether monochlorohydrins and hypochlorou acid in'the practice of this invention.

The reaction of diallyl ether monochlorohydrins with'hypochlorous acid may be performed in various ways other than those disclosed in the foregoing examples. For instance, there may be reacted a dispersion of monochlorohydrins in water with a solution containing hypochlorous acid. The same result would also be obtained by running an aqueous solution of a hypochlorite and a dilute mineral acid simultaneously into an aqueous dispersion of monochlorohydrins. 'Although the above examples disclose hypochlorite solutions of a concentration 5-6% hypochlorous acid or lower, higher concentrations may be used. Likewise, the concentration of the sulphuric acid solution may be varied provided the acid is in a suflicient amount to liberate all the available hypochlorous acid from the hypochlorite.

Other hypochlorites than sodium hypochlorite may be used for the purposes of this invention. However, when it is desired to convert the die chlorohydrins to the dioxide, it is preferred not to use a hypochlorite containing a metal whose hydroxide i essentially insoluble in strongly a1-. kaline solutions, because this may necessitate filtration of the final reaction mixture before the dioxide can be extracted.

' Somewhat higher temperatures than 10-15" C. may be employed in the addition of the hypochlorite solution to the diallyl ether monochloro hydrins. It is preferred, however, to keep the temperature at 10 C. or lower, because better yields of products are obtained.

As disclosed in Example 1, ethylene dichloride is used to remove diallyl ether dichlorohydrins from the reaction mixture. However, other 501- vents, such as chloroform or ether, may be employed. In general. any solvent which is essentially insoluble in water and which will dissolve the dichlorohydrins without being attacked by them may be used.

As disclosed previously, diallyl ether dichlorohydrins may be used fol the preparation of diallyl ether dioxide. They may also undergo various reactions to give other new and useful compounds.

It is apparent that many widely difierent embodiments of this invention can be made without departing from the spirit and scope thereof; and, therefore, it is not intended to be limited except as indicated in the appended claim.

I claim:

A proces for the preparation of diallyl ether dichlorohydrins which comprises adding to a dispersion of diallyl ether monochlorohydrins in an aqueous solution of sulphuric acid having a sulphuric acid concentration of from 10% to 25% by weight an aqueous solution of sodium hypochlorite titrating from 2.7% to 6% as hypochlorous acid by weight, the molar ratio of sodium hypochlorite to diallyl ether monochlorohydrins bein 1:1, at a temperature not in excess of 10 C., subsequently extracting the reaction mixture with a water-insoluble organic liquid which is a solvent for the resultant diallyl ether dichlorohydrins, and recovering said dichlorohydrins from said extract by evaporating said organic liquid.

OWEN CLEMENT WENTWORTI-I ALLENBY.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS 

